With the atmospheric concentration of carbon dioxide steadily increasing and little sign of a reduction in fossil fuel demand worldwide, there is a well-established need for an alternative strategy for dealing with carbon emissions from energy production. One possible solution is the accelerated weathering of ultramafic rocks. Accelerated weathering is an environmentally benign route to a thermodynamically and kinetically stable form of carbon. The chemistry is based on naturally occurring reactions and the raw materials are abundant across the earth's surface. However, the reactions are relatively slow, and achieving reaction rates sufficient to match the carbon dioxide production rate at an energy conversion facility is challenging. This work addresses a number of the challenges facing the integration of accelerated weathering with energy conversion, and presents one view of how the integration could be achieved. This work begins by developing a suite of tools necessary for investigating the dissolution and precipitation of minerals. Chapter 2 starts with a description of the minerals that will be evaluated, and then goes on to develop the techniques that will be used. The first is a differential bed reactor, which is used for measuring the dissolution rates of minerals under tightly controlled conditions. Next a bubble column reactor is developed for the investigating the adsorption of carbon dioxide and the precipitation of mineral carbonates in a single vessel. These techniques, together with a batch reactor for studying direct carbonation reactions, constitute a comprehensive set of tools for the investigation of accelerated mineral weathering. With the necessary techniques developed and proven, Chapter 3 addresses the first challenge faced by accelerated mineral weathering; the dissolution rate of magnesium from a silicate mineral. While the dissolution of this mineral is thermodynamically favorable, the kinetics are prohibitively slow. It is thought that this is because silica from the mineral tends to accumulate on the particle surface creating a passivation layer, which limits the reaction rate of the mineral. In this work, the effects of a combination of chemical chelating agents, catechol and oxalate, are evaluated for their ability to circumvent this passivation layer. The results indicate that catechol and oxalate modify the passivation layer as it forms, both accelerating the dissolution rate of the mineral and maintaining pore volume, leading to greater dissolution rates. This pore modification process is proposed as the primary mechanism by which catechol affects the passivation layer. The combination of catechol and oxalate under acidic conditions is also shown be effective when the ambient solution approaches the saturation point of silica. Finally, the chelating does not impede the precipitation of carbonate products, a critical hurdle for a carbon storage process. The chelating agent work is extended in Chapter 4, with a sensitivity study that evaluates the response of the dissolution rate to changes in both pH and the concentration of the chelating agents. Oxalate and pH are found to exhibit a strong influence on the mineral dissolution rate, while the effect of catechol is more apparent after significant dissolution has taken place. These observations are in agreement with the model of passivation layer modification proposed. In addition, some alternatives to the chelating agent catechol are evaluated. It is found that when used in combination with oxalate, these alternatives appeared equivalent to catechol, but alone they had only a minor effect. Catechol was also noted to have a significant effect on the dissolution rate of iron from the silicate mineral, and a mechanism for this effect was proposed. The direct adsorption of carbon dioxide and precipitation of solid carbonates in a single reaction step presents another challenge for accelerated mineral carbonation. In general, the magnesium carbonates formed at ambient pressure and moderate temperatures tend to be hydrated, and at times contain unused hydroxides, leading to inefficiencies in both transport and storage. It is shown in Chapter 5 that by seeding reaction vessels with the anhydrous form of magnesium carbonate, it is possible to grow this desired phase with minimal formation of the metastable hydrated phases. The formation of this phase is primarily limited by the precipitation rate, but in some situations, carbon dioxide hydration kinetics and magnesium hydroxide precipitation kinetics also play a role. In Chapter 6, these developments in both magnesium silicate dissolution and carbonate precipitation are combined into a proposed technology for the direct capture and storage of carbon dioxide. This application of accelerated mineral weathering is shown to significantly reduce the carbon emissions of an energy conversion technology through life cycle assessment. This novel approach to the mitigation of carbon emissions presents a compelling argument for the continued development of accelerated mineral weathering as a combined carbon capture and storage technology.

Rising concentration of CO2 in the atmosphere is attributed to increasing consumption of fossil fuels. One of the most effective mechanisms to store CO2 captured from power plants is via geological injection of CO2 into formations that contain calcium and magnesium silicate and alumino-silicate minerals and rocks. The mechanism that ensures permanent storage of CO2 within rocks is mineral carbonation. When CO2 is injected into mineral or rock formations rich in calcium or magnesium silicates, they react with CO2 to form calcium or magnesium carbonates, which is also known as carbon mineralization. Calcium and magnesium carbonates are stable and insoluble in water. However, the kinetics of in-situ mineral carbonation involve CO2 hydration, mineral dissolution and formation of carbonates, and the relative rates of these phenomena when coupled, are not very well understood. In this study, the coupled interactions of CO2-reaction fluid-minerals were investigated to determine the optimal conditions for carbon mineralization, and to identify the chemical and morphological changes in the minerals as they react to form carbonates. Carbon mineralization in various minerals and rocks such as olivine ((Mg,Fe)2SiO4)), labradorite ((Ca, Na)(Al, Si)4O8), anorthosite (mixture of anorthite (CaAl2Si2O8), and basalt (rock comprising various minerals) were studied at high temperatures (Tmax = 185 oC) and high partial pressures of CO2 (PCO2, max = 164 atm) which are relevant for in-situ conditions. These minerals and rocks differ considerably in their chemical compositions and reactivity with CO2. A systematic comparison of the effects of reaction time, temperature, partial pressure of CO2, and fluid composition on the conversion of these magnesium and calcium bearing minerals and rocks showed that olivine was the most reactive mineral followed by labradorite, anorthosite, and basalt, respectively. Previous studies at Albany Research Center (Gerdemann et al., 2007; O'Connor et al., 2004) reported that a solution of 1.0 M NaCl + 0.64 M NaHCO3 was effective in achieving high extents of carbonation in olivine, heat-treated serpentine, and wollastonite. However, the independent effects of NaCl and NaHCO3 and their role in mineral carbonation were not sufficiently explained. In this study, the role of varying concentrations of NaCl and NaHCO3 on carbon mineralization of various minerals was elucidated. NaHCO3 buffered the pH and served as a carbon carrier, resulting in higher carbonate conversions. Except in the case of olivine, NaCl had a negligible effect on enhancing mineral carbonation. Unlike NaHCO3, NaCl does not buffer the pH or serve as a carbon carrier, but Cl- may serve as a weak chelating agent can complex with Mg or Ca in the mineral matrix to enhance dissolution. The competing effects of ionic strength and pH swings as the mineral dissolves and carbonation further complicate the role of NaCl on mineral carbonation. Based on the experimental methodologies developed to study carbon mineralization in minerals and rocks at high temperatures and pressures, alternative applications such as the remediation of hazardous alkaline wastes such as asbestos containing materials were identified. Asbestos is composed of chrysotile, a fibrous hydrated magnesium silicate mineral and a form of serpentine known to cause respiratory illnesses. By treating asbestos containing materials with CO2 in the presence of 0.1 M Na-oxalate, dissolution of chrysotile and precipitation of newer phases such as glushinkite (Mg(C2O4)* 2H2O) and magnesite (MgCO3) occurred, which reduced the chrysotile content in asbestos. Based on the methodologies for studying mineral dissolution and carbonation kinetics, and coupled mineral dissolution and carbonation behavior, a scheme for connecting laboratory scale experiments with simulations to estimate the uncertainties associated with carbon mineralization was developed. The effects of temperature, different dissolution rates, and varying levels of surface area changes due to passivation or reactive cracking on the rates of carbon mineralization were simulated using PhreeqC, a computer program developed for geochemical speciation calculations (Parkhurst & Appelo, 1999). Various studies proposed that microfractures and cracks may occur in geologic formations due to the extensive growth of carbonate crystals (Kelemen & Hirth, 2012; Kelemen & Matter, 2008; Matter & Kelemen, 2009; Rudge et al., 2010). Other studies have suggested that the formation of carbonates may plug the pore spaces and limit further reactivity (Hövelmann et al., 2012; King et al., 2010; Xu et al., 2004). The effects of changes in surface area due to the formation of microfractures or passivation due to carbonate growth on the rates of carbon mineralization were also simulated. Overall the results of these studies demonstrate the effect of various parameters on carbon mineralization and how these parameters can be connected to predict CO2 storage in mineral formations. The frameworks to connect laboratory scale experiments with simulations to determine carbon mineralization rates and to assess the risks associated with CO2 injection in reactive formations, can be used to direct future research efforts to predict the fate of injected CO2 with greater accuracy for sensor placement and optimization of CO2 monitoring technologies.

With the increase of the the global energy consumption has also been increasing, which is about 18 TW nowadays (Dudley, 2018), the anthropogenic CO2 emissions have also been increasing, which is about 410 ppm nowadays (Dudley, 2018; Tans & Keeling, 2019). Numerous evidences have been reported indicating that high atmospheric CO2 concentration can have significant greenhouse effect and thus lead to global warming and climate change (Pachauri et al, 2014; Hansen et al, 2013). Therefore, measures need to be taken to control and reduce the atmospheric CO2 concentration. In such circumstance, carbon capture, utilization and storage (CCUS) technologies have been proposed and developed to close the carbon cycle. Mineral carbonation (MC) is one of the CCUS technologies, which mimics the natural silicate weathering process to react CO2 with silicate materials so that carbon can be stabilized in the form of insoluble carbonates for permanent carbon storage (Seifritz, 1990; Lackner et al, 1995). Both Ca- or Mg-bearing silicate minerals and alkaline silicate industrial wastes can be employed as the feedstock for mineral carbonation (Sanna et al, 2014; Gadikota et al, 2014; Park, 2005; Park & Fan, 2004; Park et al, 2003; Park & Zhou, 2017; Zhou, 2014; Zhao, 2014; Swanson, 2014). While they share similar chemistries and total Mg and Ca contents, different MC feedstock can lead to different challenges for CCUS. As for silicate minerals, although they have large enough capacity to mineralize all the anthropogenic CO2 emissions, their reactivities are generally very low, and measures should be developed to accelerate the carbonation kinetics of the minerals (Sanna et al, 2014). However, the elemental extraction of the silicate minerals is a relatively complicated kinetic process, because silica-rich passivation layer can form on the particle surface during mineral dissolution process and thus the rate-limiting step of the process can change from chemical reaction to mass transfer. Without a clear understanding of the elemental extraction kinetics, the design and evaluation of different acceleration methods aiming at different rate-limiting steps of the process can be challenging. As for alkaline industrial wastes, they are generally more reactive than silicate minerals, but can be more heterogeneous with more complicated compositions. In such cases, the separation and recovery of other elements should also be integrated with the carbonation process so that the overall sustainability of the mineral carbonation technology can be enhanced. In order to address these challenges, this study focused on the fundamental understanding of dissolution and carbonation behaviors of alkaline silicate materials and integration of step-wise separations of rare-earth elements (REEs). Both experimental and modeling studies were carried out to provide insights into how Mg and Ca as well as REEs are leaching into solvents at different conditions, and the fundamental understandings on mineral dissolution kinetics and mechanisms were also put forward. The fate of REEs in different product streams was also identified, and methods were developed and optimized to recover and concentrate REEs, while producing solid carbonates with highest purities. Hopefully, the findings in this study can not only advance the carbon mineralization technology but also contribute to the utilization and extraction of alkaline metals, as well as REEs, from other complex unconventional resources for the sustainable energy and material future.

Compreender os ciclos de nutrientes e a dinâmica da matéria orgânica no ecossistema da Amazônia é essencial para o domínio do manejo eficiente da floresta e do solo. O desaparecimento de florestas tropicais, acompanhada de acelerados processos de perda de solo e de matéria orgânica, pelo desmatamento, queimadas e avanço da fronteira agrícola despertam preocupações. As características das substâncias húmicas remetem aos processos de gênese da matéria orgânica, à capacidade de sustentabilidade para os usos múltiplos em cultivos e aparece como indicador da qualidade do solo. O objetivo deste trabalho foi relacionar as características das substâncias húmicas do solo com o seqüestro de carbono em sítios de floresta em clímax, em área moderadamente e intensamente antropizada, ambientes de influência da Rodovia BR-163 - Cuiabá-Santarém, região que experimenta um incremento das ações antrópicas em função do anúncio da pavimentação desta rodovia. Foram determinadas as características das substâncias húmicas pelas técnicas de espectroscopia no infravermelho com transformada de Fourier (FTIR), análise elementar, espectroscopia de fluorescência de luz no UV/Visível, espectroscopia de absorção de luz no UV/Visível, espectroscopia de ressonância magnética nuclear (RMN) e espectroscopia de ressonância paramagnética eletrônica nuclear (EPR). Os resultados de infravermelho das substâncias húmicas do solo do sítio de floresta em clímax, indicam alta complexidade no arranjo conformacional, denotando-se a presença de elevada humificação do material orgânico, o que é corroborado pelos resultados de fluorescência, onde as características das substâncias húmicas deste ambiente apresentaram maior policondensação e grau de humificação. Utilizando-se a espectroscopia de absorção de luz no UV/Visível, constatou-se que a razão E4/E6 é de 2,27 para solo do ambiente de floresta em clímax. Esse é o menor valor das três frações, o que demonstra que as substâncias húmicas deste sítio estão em estágio elevado de policondensação e apresentam maior quantidade de estruturas aromáticas. Os resultados de RMN indicam que a maior percentagem de carbono aromático está exatamente nas substâncias húmicas do solo do sítio de floresta em clímax. Os resultados de EPR demonstram também que as substâncias húmicas dos solos dos sítios em clímax apresentam maiores números de radicais livres do tipo semiquinona (7,52) dos três ambientes estudados. As substâncias húmicas provenientes dos solos dos sítios com intensa atividade antrópica indicam a presença de menor grau de humificação, pelo número de radicais livres do tipo semiquinona (4,68), menor valor dos três ambientes estudados. Desta forma, as características das substâncias húmicas do solo de ambientes em clímax, pela elevada aromaticidade, policondensação e grau de humificação, proporcionam aumento da biodiversidade, incremento da produtividade, melhoria da estrutura deste solo, contribuindo junto à formação de fração húmica não lábil, bem como maior estabilidade dos complexos organominerais, condições favoráveis para o seqüestro de carbono e mitigação do aumento do efeito estufa. / Understanding the cycles of nutrients and organic matter dynamics in Amazons ecosystem is essential for the domain of efficient management of the forest and soil. The disappearance of tropical forests, accompanied by processes of accelerated loss of soil and organic matter, for the deforestation, forest fires and advancement of agricultural frontier arouse concerns. The characteristics of humic substances refer processes of genesis organic matter, capacity of sustainability for multiple uses in cultures appears as indicator the quality of the organic matter. The objective of this work was to relate the characteristics of humics substances in the soil, with the carbon sequestration in sites of forest in climax, in moderately and intensely area in humans use, environments in Influence of highway BR-163 - Cuiaba-Santarem, a region experiencing an increase in action of the human being according to the announcement of paving the road. There were certain characteristics of humic substances by the Fourier transform infrared (FTIR) spectroscopy, elemental analysis, ultraviolet-visible fluorescence spectroscopy, ultraviolet-visible absorption spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and electronic paramagnetic resonance (EPR) spectroscopy. The results of infrared of humic substances in soil site of a climax forest, show high complexity in conformal arrangement, showing up the presence of high humification of organic material, which is corroborated by the results of fluorescence, where the characteristics of humic substances this environment polycondensation and had greater degree of humification. Using ultraviolet-visible absorption spectroscopy, it was found that the reason E4/E6 is 2.27 for the environment of forest in climax. This is the lowest of the three fractions, which shows that the humic substances from this site are in high stage of polycondensation and the greatest amount of aromatic structures. The results of NMR indicate that the highest percentage of carbon aromatic is exactly humic substances in soil from site of forest in climax. The results of EPR also demonstrate that the soil humic substances in climax\'s sites show the highest numbers of free radicals semiquinonas type (7.52) in the three kinds of environments studied. The humic substances from the soil of sites with intense human activity indicate the lesser presence of degree humification, for the number of free radicals semiquinona\'s type (4.68), lower value of the three environments studied. Thus, the characteristics of humic substances in soil from environments in the climax for the high aromaticity, polycondensation and degree of humification, provide an increase of biodiversity, increasing productivity, improving the structure of the soil, contributing next to the formation of humic fraction not labile, greater stability of organic minerals complexes, favourable conditions for carbon sequestration and mitigation of increased greenhouse effect.

Carbon Capture and Storage (CCS) technology could help reduce anthropogenic CO2 emissions to the atmosphere. So far, CCS has failed to attract government support in the UK due to high costs of implementation. The broad deployment of CO2-EOR could aid the development of CCS by providing additional revenue streams for investors. The success of the CO2- EOR in the United States has raised the question of whether this success could be replicated in the UKCS. This thesis answers these questions by introducing two distinct models, which analyse the similarities and differences between the two oil provinces from the subsurface and economic perspectives. The first model integrates into the economic framework the behaviour of oil and CO2 in a reservoir. The model is applied to an oil field in the North Sea. It analyses whether the screening criteria developed based on the onshore US experience to screen for oil field candidates for the CO2 would be suitable for the oil fields in the UKCS. The second model is a theoretical CO2-EOR with storage model, which analyses how the inclusion of permanent storage changes the economics of CO2-EOR. The CO2-EOR with storage model allows for an endogenous switching point between the CO2-EOR and the permanent CO2 storage phase depending on the various economic factors, such as oil prices, sequestration subsidies and fees, CO2 price, and oil and gas tax rates. The CO2-EOR with storage model shows different behaviour compared to the case without permanent storage. On the policy level, the main difference between the two countries revealed that the UK strongly focuses on cutting CO2 emissions while the U.S. on boosting domestic oil production. Therefore, the third study in this thesis investigates the net carbon footprint of the CO2-EOR activity in the North Sea.

The demand for energy continues to grow but concerns over climate change means that conventional fossil fuels will eventually need to be replaced. The solution to the energy crisis will require a combination of both conventional energy sources with CO2 capture and renewable technologies. While many renewable technologies exist, it is not common that CO2 capture is incorporated into the process. Biomass is an ideal feed-stock for bio-energy production as it is CO2 neutral. Many thermochemical conversion technologies exist, but the Alkaline Thermal Treatment (ATT) reaction is particularly interesting because it combines conventional thermochemical conversion with CO2 capture in order to create a process that is potentially CO2 negative. By reacting biomass with a metal hydroxide, high purity H2 can be produced while simultaneously locking the carbon as a stable carbonate, which is a form of Bio-energy with Carbon Capture & Storage (BECCS). The H2 can then be used for applications ranging from Fischer-Tropsch synthesis to PEM fuel cells. Group I & II hydroxides were investigated for their ability to react with cellulose (a biomass model compound) in the ATT reaction scheme. Comparison between both groups indicated that NaOH and Ca(OH)2 were the best hydroxides from groups I & II respectively. However, the amount of H2 produced during the ATT of cellulose with Ca(OH)2 is considerably lower than with NaOH. A 10% Ni/ZrO2 catalyst was then added to increase the yield of H2 from the reaction between cellulose and Ca(OH)2. It was found that at 20% catalyst loading, the amount of H2 produced and the suppressed level of CO2 was similar to the ATT with NaOH. Several other catalytic metals were also investigated and found to have the following H2 production activity: Ni > Pt≈Pd > Co > Fe, Cu. Since Ni was the most active and has a considerably lower cost than noble metals it was chosen for additional studies. The ATT reaction in the presence of Ni has two distinct steps in the formation of H2 from cellulose. The presence of Ca(OH)2 enhances the formation of linear oxygenates from cellulose. These oxygenates are then reformed over the Ni-based catalyst to H2 and CO2, the latter of which is captured by Ca(OH)2 to form CaCO3. If either Ca(OH)2 or Ni was removed from the reaction, the yield H2 fell significantly. Although the reactants and the catalyst are all solid materials, they do not need to be physically mixed. The Ni-based catalyst produced H2 primarily through the reforming of gaseous species and therefore could be placed ex-situ of the cellulose and Ca(OH)2 mixture. However, placing the catalyst away from Ca(OH)2 prevented CO2 capture. In order to remedy this Ca(OH)2 was mixed with the Ni-based catalyst and mixture was placed ex-situ of pure cellulose. This created a process whereby cellulose could be decomposed thermally followed by a single gas-phase Alkaline Thermal Treatment (GATT) reforming step of the pyrolysis vapors to H2 with suppressed CO2.

Proveniente do processo de pirólise, o biochar é constituído por elevado teor de carbono, em estruturas que são responsáveis pela elevada resistência à degradação. O material vem sendo objeto de estudo por seus diversos usos e benefícios que oferece ao ambiente. Quando aplicado ao solo traz melhorias relacionadas às propriedades químicas, físicas e microbiológicas do mesmo, além de ser ferramenta para o sequestro de carbono, alternativa para disposição de resíduos orgânicos com concomitante produção de energia. Entretanto, as propriedades químicas e físicas dos biochars variam grandemente devido à diversidade de matérias-primas e das condições de produção. O presente estudo visou avaliar a variação das propriedades físicas, químicas e morfológicas do biochar e a influência da matéria-prima e da temperatura de pirólise na caracterização final do produto. Para tanto, foram produzidos biochars oriundos da combinaçao de quatro temperaturas (350, 450, 550 e 650 °C) e de quatro matérias-primas (palha de cana-de-açúcar, casca de arroz, dejeto de galinha e serragem). Em todos os produtos e materiais de origem foram feitas avaliações de pH, condutividade elétrica (C.E.), capacidade de troca catiônica (CTC), teor de carbono (C), nitrogênio (N), hidrogênio (H), material volátil e cinzas, teor de nutrientes, além de avaliação de espectroscopia através de Infravermelho por Transformada de Fourier (FTIR), análise de morfologia por Microscopia Eletrônica de Varredura, análise de termogravimetria e teores de lignina celulose e hemicelulose. Constatou-se variação de algumas proprieades químicas como os teores de C, H, O, materiais voláteis, cinzas, carbono fixo, índice pH, condutividade elétrica e capacidade de troca catiônica com maior influência da temperatura de pirólise. O teor inicial de macro e micronutrientes presentes nas matérias-primas apresentou maior influência na variação das concentrações desses nutrientes nos biochars. De forma geral observou-se aumento da estabilidade química nos diferentes biochars com a elevação da temperatura de pirólise. A recalcitrância dos biochars confere-lhes persitência no solo e é confirmada pelo aumento dos teores de C e diminuição da emissão de CO2 nos tratamentos com adição desses materiais em comparação com adição de suas respectivas matérias-primas. Ademais, a contribuição dos biochars para elevação no pH do solo é de fundamental importância para sua adoção na agricultura sob o ponto de vista de fertilidade do solo. / A product of pyrolysis, biochar is a carbon rich material and its structure is responsible for the high resistance to degradation. Biochar is an interesting object of study due to its diverse applications and amendments to the environment. When applied to the soil, it is able to enhance soil physical, chemical and microbiological properties. It is also pointed as an instrument to sequester carbon and an alternative disposal for organic residues as well as energy source. However, the resultant properties of biochar vary greatly considering the diverse options of feedstocks combined with the contrasting production conditions used to obtain the final product. The present study aimed the evaluation of the different chemical and physical properties within a range of diverse biochars, and the assessment of feedstock or pyrolysis temperature mediated changes. The biochars produced combined pyrolysis temperatures (350, 450, 550 and 650 °C) with four feedstocks (sugar cane straw, rice husk, poultry manure and sawdust). In order to assess biochar properties and the temperature or feedstock mediated changes, several analysis were performed in the feedstock and biochars produced. The analysis included pH, cation exchange capacity, carbon, nitrogen and hydrogen content, proximate analysis, nutrient content, as well as spectroscopy performances such as Fourier Transformed Infrared (FTIR), morphological assessment through Scanning Electron Microscopy (SEM), termogravimetric analysis and lignin, cellulose and hemicellulose contents. The results suggests that temperature influenced greatly some of the chemical properties assessed, such as the contents of C, H, O, volatile matter, ash, fixed C, pH, electrical conductivity, cation exchange capacity. Feedstocks initial macro and micronutrient contents exhibited more influence in the variation of these elements in the biochars. In general, there was an increase in chemical stability in the different biochars with increasing pyrolysis temperature. The high recalcitrance found in biochars enable them to persist within the soil, which was confirmed by the increased levels of C content and decreased CO2 emissions when biochars addition was compared with their feedstocks addition to soils. Moreover, the contribution of biochar in increasing soil pH is very important from a soil fertility standpoint.

A recuperação e a restauração florestal de ecossistemas degradados podem não acontecer das maneiras desejadas, se houver carência nutricional ou suprimento inadequado de nutrientes às plantas no estádio inicial de desenvolvimento de espécies florestais nativas. O objetivo da presente investigação foi avaliar os efeitos da deficiência de nutrientes nas plantas na fase inicial de desenvolvimento das espécies florestais nativas Schinus terebinthifolius Raddi (aroeira-pimenteira), Cordia superba Cham. (baba-de-boi) e Cariniana estrellensis (Raddi) Kintze (jequitibá-branco). Foram observadas as alterações ultra-estruturais e teciduais das células do mesofilo das folhas, foi descrita a sintomatologia visual de deficiência nutricional, foram feitas as determinações de teores de macro e micronutrientes, das taxas de assimilação de gás carbônico e de transpiração, e as mensurações da altura e da produção de biomassa. O experimento foi conduzido em casa de vegetação, em blocos ao acaso, com três repetições e treze tratamentos para cada espécie, empregando a técnica de diagnose por subtração (-N, -P, -K, -Ca, -Mg, -S, -B, -Cu, -Fe, -Mn, -Mo, -Zn), sendo que em um dos tratamentos, as espécies nativas foram cultivadas em solução nutritiva completa, com todos os macros e micronutrientes. Durante o experimento e em sua análise, foi observada a seqüência de eventos que motivaram os sintomas de deficiência e a diminuição na produção de biomassa. Sabe-se que falta de um nutriente provoca alteração molecular, o que alterou as ultraestruturas celulares das folhas que foram observadas por microscopia. Essas modificações celulares provocaram alterações no tecido vegetal que induziram nas plantas os sintomas visuais específicos de cada nutriente que foram descritos. Como efeito fisiológico da deficiência nutricional, de forma geral, constataram-se diminuições nas taxas de fotossíntese e de transpiração e, por conseguinte, na produção de biomassa. Estes resultados claramente evidenciam o fato de que projetos de implantação de florestas ou de recuperação e restauração de ecossistemas degradados por meio do plantio das três espécies florestais nativas, em solos que necessitem de suplementação nutricional, poderão ter seu sucesso comprometido se não houver complementação nutricional / The recovery and forest restoration of degraded ecosystems may not be occur as desired if there is a nutritional deficiency or an inadequate supply of nutrients in the initial phase development of native forest species. The objective of this research was to evaluate the macronutrient and micronutrient deficiency effects on Brazilian native species young plants: Schinus terebinthifolius Raddi, Cordia superba Cham. and Cariniana estrellensis (Raddi) Kintze. Ultrastructural and tissue of the mesophyll cells of leaves changes were observed by microscopy, the visual symptom of nutritional deficiencies were described, the nutrient contents were analyzed, the carbon assimilation and transpiration rates were measured, the plant heights and the biomass production were measured. The experiment was carried on a greenhouse in a randomized block design with three replications and thirteen treatments for each species, using the technique of diagnosis by subtraction (-N, -P, -K, -Ca, -Mg, -S, -B, - Cu, -Fe, -Mn, -Mo, -Zn) and in one of the treatments the species were grown in a nutrient solution with all macro and micronutrients. It was observed, during the experiment and its analysis, a sequence of events that caused the visual symptoms and decreased the biomass production. It is known that the nutrient deficiency causes molecular alterations, which consequently led the changes in cellular ultrastructure of the leaves and they were observed by microcopy. These cellular changes caused modifications in the foliar tissue, and the plants showed specific visual symptoms of each nutrient, which they were described. As physiological effect of nutritional deficiency, in general decreases the photosynthesis and transpiration taxes, and consequently the biomass production were decreased. These results clearly project that forest implantation or recovery and restoration of damaged ecosystems by planting the three native species in soils that require nutritional supplementation may have its success compromised if there is no a nutritional supplementation

A agricultura pode ser uma aliada importante para a mitigação da concentração de gás carbônico (CO2) na atmosfera. Pela fotossíntese pode-se converter o CO2 da atmosfera em massa vegetal, e, além disso, por meio de um manejo adequado desta massa pode-se reter parte do carbono (C) no solo, caracterizando um \"seqüestro de C\" da atmosfera pelo solo. Pesquisas têm se voltado para entender o papel da produção agrícola, como os sistemas conservacionistas de manejo, ou seja, o plantio direto (PD), e das pastagens de Brachiaria sobre a dinâmica do C no solo. Estudos sobre a dinâmica e a estabilidade da matéria orgânica do solo (MOS) são necessários, já que variáveis como estoques de carbono (EC) e graus de humificação podem ser avaliados, e sendo assim, obter parâmetros fundamentais para a mitigação de CO2 na atmosfera, tema que se insere num dos enfoques das Mudanças Climáticas Globais. Nesse contexto, espectroscopias, como por exemplo, a Ressonância Paramagnética Eletrônica (RPE), a Fluorescência de luz no ultravioleta-visível (UV-vis) e a Fluorescência Induzida por Laser (FIL) podem ser fundamentais na avaliação da estabilidade da MOS. Este trabalho teve como objetivo verificar o comportamento da MOS em áreas com potencial para seqüestro de C, por meio da avaliação dos estoques deste no solo, em diferentes sistemas de manejo e posterior caracterização por Espectroscopia. Além disso, e em função das dificuldades encontradas na seleção da melhor metodologia para a quantificação de C, foi também possível avaliar métodos de determinação de C, comparando-os entre si pelos coeficientes de variação e análise multivariada, e assim propondo uma melhor metodologia. Em área tropical de pastagens de Brachiaria decumbens, no Brasil, os resultados mostraram que a determinação dos EC foram maiores nesses sistemas, comparado com a vegetação nativa de cerradão, após 27 anos de experimento. Os maiores EC obtidos pelas pastagens foram favorecidos pela constante entrada de material vegetal na superfície do solo, também influenciado pela entrada do nitrogênio (N), além do sistema radicular da gramínea, considerando o tratamento de pastagem com adição anual de N e aplicação de 2 t ha-1 de calcário (com reforço de 1 t ha-1 anual), o melhor tratamento em função do acúmulo da MOS. Os resultados mostraram que essas pastagens bem manejadas podem possibilitar um seqüestro de 6,1 a 12,8 Mg CO2 ha-1 ano-1 da atmosfera. Com a avaliação qualitativa da MOS, também foi possível obter resultados promissores na determinação da estabilidade da MOS. A detecção do aumento do conteúdo de C no solo foi acompanhada pela redução do grau de humificação, por meio da FIL. Esta redução na humificação foi devido à entrada de material orgânico mais lábil, ou seja, menos transformado. Na Fluorescência convencional e RPE, com amostras de AH em solução, os maiores graus de humificação foram obtidos para os AH dos tratamentos de pastagem, principalmente os que tiveram adição de calagem. O Ca2+, além de aumentar a atividade microbiana, pode complexar com os AH, associado ao aumento da estabilidade da MO. No sistema de PD de soja com renovação de cana-de-açúcar, os maiores teores de C foram obtidos nas amostras referentes aos sistemas sob PD após 7 anos sob esse manejo, em comparação com áreas sob manejo convencional. O acúmulo de MOS foi devido principalmente à preservação da cobertura vegetal associada com o não revolvimento do solo, rotação de culturas e a não queimada da cana-de-açúcar. Nessa área experimental, foi possível constatar um seqüestro de 0,15 a 5,29 Mg CO2 ha-1 ano-1 da atmosfera. Com relação à estabilidade da MO avaliada por Espectroscopia de FIL, verificou-se que o sistema de PD apresentou menor grau de humificação, devido à maior entrada de material orgânico lábil. Os resultados obtidos em área experimental de PD com grãos, com até 22 anos de duração, estão provavelmente associados com o tipo de solo analisado. Nos Latossolos com alto conteúdo de argila pode haver proteção física da MO, provavelmente impedindo alterações estruturais desse material, mesmo após longo período sem o revolvimento do solo. Outro fato importante é que o estudo de seqüestro de C depende muito da área avaliada, ou seja, delineamento do experimento, histórico do local, duração, condições climáticas, taxas de decomposição do C, produção de massa vegetal e aporte de resíduos. / Agriculture can play an important role in mitigating carbon dioxide (CO2) concentration in the atmosphere. Through photosynthesis, it is possible to convert CO2 from atmosphere to plant biomass, and moreover, through an adequate agricultural system CO3 can be stored in soil, characterizing \"carbon sequestration\". Nowadays, many researches want to understand the role of agriculture production, as no-tillage, and Brachiaria pastures, in carbon dynamics in soil. Studies about organic matter dynamics and stability are necessary, since variables such as carbon stocks and degree of humification can be evaluated, and as a result, to obtain essential parameters to CO2 mitigation to the atmosphere. This topic is inserted in some Global Climate Change interests. In this context, spectroscopic methods, for example, Electron Paramagnetic Resonance (EPR), UV-Vis light fluorescence and Laser Induced Fluorescence (LIF) can be fundamental in the stability of soil organic matter (SOM) evaluation. The present study aims to examine the SOM behavior in areas with carbon sequestration potential, through evaluation of carbon stocks in soils, in different tillage systems followed by characterization by spectroscopy. Therefore, the knowledge of the organic matter (OM) quantity is important in soil management regarding to a sustainable agriculture. However, little consistent information is found to compare and recommend the most adequate method to obtain satisfactory results for each study. Consequently, it was possible to evaluate the OM quantity in Oxisols by different methods and compare them, using coefficient of variation and principal component analysis, to propose the best methodology. In the tropical regions of Brazil, in Brachiaria decumbens pastureland, the results showed that the greatest SOM content occurred under pastureland, against the native dense Cerrado vegetation, after 27 years of experiment. The highest carbon stocks obtained by pasture samples were favored by accumulations of plant biomass on the soil surface, nitrogen input, besides Brachiaria root systems. According to the results obtained, the annual input of adequate amounts of limestone (2 t ha-1 addition and 1 t ha-1 year-1 reinforcement) and N seemed to be the best treatment regarding different pastureland treatments, mainly due to its higher C accumulation. The results also showed that non-degraded pastures can enable an annual sequestration rate ranging from 6.1 to 12.8 Mg CO2 ha-1 year-1. Qualitative evaluation of SOM also obtained satisfactory results on the soil surface. Results showed that higher C amount was followed by lower degree of humification, obtained by LIF. This lower humification was due to labile organic material, or greater fresh input of crop residues. In conventional fluorescence and EPR, with humic acids, the greatest degree of humification was obtained in pastures treatments, especially in treatments with lime input. Ca2+, in addition to increasing the biological activity, can combine with humic acids, increasing OM stability. In the no-tillage system of soya and sugar cane renovation, higher C amounts were obtained in no-tillage samples, after 7 years of experiment. The maintenance of a permanent vegetal cover, without soil disturbing and without sugar cane burning was essential to SOM accumulation against conventional management. In the no-tillage system, in a period of 7 years, it was possible to verify a sequestration rate ranging from 0.15 to 5.29 Mg CO2 ha-1 year-1. In relation to SOM stability by LIF, no-tillage presented lower degree of humification, due to input labile OM. The results obtained under no-tillage cropping system after 22 years are probably associated with the kind of soil analyzed. In Latossols, with high amount of clay, there may be a physical protection of OM, probably preventing structural changes in this material, even after a long period without soil disturbing. Another important factor is that C sequestration studies depend on the evaluated area, such as experiment outline, historical area, time, climate conditions, C decomposition rates, vegetal biomass production and residue input.

In order to fully understand the magnitude of the benefits that forests provide, it is crucial to understand the full suite of ecosystem services that they offer. A southern Appalachian red spruce-Fraser fir forest was intensively analyzed using a variety of methodologies to determine the nature and quantity of some of these services. Many hypotheses exist regarding the future of these spruce-fir forests, which were heavily disturbed by the non-native balsam wooly adelgid during the 1980s. Direct measurements over the course of a decade assessed these hypotheses and indicate that this forest is recovering structure and function. The forest is accruing overstory biomass, with vegetation composition on a trajectory towards historic conditions. By using a total forest inventory of all vegetation from overstory trees to understory mosses, rates of productivity and nutrient cycling were determined. Productivity of this forest at low elevations has returned to pre-adelgid levels, while at high elevations productivity is approaching these levels. In the absence of an intact overstory, forest understory vegetation can compensate by disproportionately cycling and retaining nutrients such as nitrogen that would otherwise leach offsite. The understory of this forest provides an important service in nutrient cycling. Our ability to actively manage forests in order to manipulate levels and rates of carbon sequestration was assessed using stand data and the Forest Vegetation Simulator Growth and Yield Model. Silvicultural intervention proved effective at sequestering additional carbon over a no action alternative by the end of our simulation period. This forest provides a variety of ecosystem services and has retained its ability to recover their function after catastrophic disturbance.